Coordination Chemistry of Polyoxovanadates as Inorganic Ligands

Hayashi, Yoshihito

doi:10.4019/bjscc.66.12

Cited by 13 publications

(16 citation statements)

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“…Given the high charge of this anion, aw ater solvation shell was constructed, defined by van der Waals radii of the constituent atoms. [65] The addition of two electrons to ad iamagnetic {V 14 }c lusters ees each one localised at either end of the molecule, specifically,V 1w hichs its at the centre of aV O 5 Fo ctahedron that is linked to two edge-shared VO 5 Fo ctahedra (V4a nd V4A;F igure S5), and two corner-shared VO 5 polyhedra (V5 and V5A;F igure S5). The latter are squarep yramidal units that ultimately connect each {V 3 F} cap, providing the bondingpathway that links the two unpaired electrons.T here are two singly-occupied molecular orbitals (SOMO) that possess 56.3 %d xy character from V1 and V1' (Figure7).…”

Section: Dft Calculationsmentioning

confidence: 99%

“…[1] Within the large polyoxometalate family,which is mainly constructed by vanadium, molybdenuma nd tungsten centres in their high oxidation states, mixed-valent polyoxovanadate clusters are one of the most interesting subgroups, due to their complex equilibriao f ride and oxofluoride chemistry is the tendency for polymerisation, and formation of products which exhibit 2D and 3D structures constructed by oligomeric, chain and ladder shaped buildingb locks. [2,5,15,16] Moreover,t he formation of these structures has been achieved under hydrothermal conditions, which is known for the complexity of this reaction domain, [15,17] and the associated inherent difficulties in understanding the assembly process. Interestingly,t he reported higher nuclearity molecular polyoxofluorometalates are quite rare.…”

Section: Introductionmentioning

confidence: 99%

“…numerouss peciesa nd rich redox chemistry which is reflected to unique catalytic properties, magnetic behaviour and energy storagea pplications. [2][3][4][5][6] The assembly of vanadate clusters in aqueousmediumhas been studied extensively,a nd the reported structures include aw ide range of nuclearities and structural motifs such as [V 3 O 9 ] 3À ,[ V 5 O 14 ] 3À ,[ V 8 O 14 ] 4À ,[ V 12 O 32 ] 4À , [V 13 O 34 ] 3À ,[ V 15 O 42 ] 9À ,[ H 2 V 16 O 39 ] 7À and [V 34 O 82 ] 10À . [7,8] Most of these clusters exhibit closeds phere-like structures, [8][9][10] and only [V 12 O 32 ] 4À has an open, bowl-shaped framework that can act as ah ost.…”

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confidence: 99%

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Design and Assembly of Covalently Functionalised Polyoxofluorovanadate Molecular Hybrids

Nicolaou

Papanikolaou

Tsipis

et al. 2018

Chemistry A European J

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Mixed-valent polyoxometalate (POM) clusters are one of the most interesting host species, showing a wide range of structural features and properties. The facile preparation and functionalisation of a mixed-valent polyoxofluorovanadates is reported, where two electrons are trapped to antipodal sites of the clusters. The first members of this family of clusters with the general formula, [V V O (μ-O) (μ -O) (μ -F) (L) ] , where L: py=pyridine (1); pyr=pyrazine (2); im=imidazole (3), are unique organic-inorganic hybrids with the addition of a N-donor ligand at either end of the polyoxofluorovanadate. The composition and connectivity of 1-3 were characterised by single-crystal X-ray diffraction and electrospray ionisation mass spectrometry. Electron paramagnetic resonance spectroscopy revealed that the two well-separated V ions in each cluster are fully uncoupled with J=0, giving a degenerate singlet-triplet ground state. This attenuation of the exchange interaction is probed with density functional theoretical calculations that reveal that the inclusion of the fluoride ion in the cluster produces a bond pathway biased toward destructive interference between competing ferromagnetic and antiferromagnetic interactions. These robust molecular materials are the ideal combination of desirable electronic properties, with an organic handle with which they can be integrated into spintronic circuitry for molecular devices.

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Section: Dft Calculationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Design and Assembly of Covalently Functionalised Polyoxofluorovanadate Molecular Hybrids

Nicolaou

Papanikolaou

Tsipis

et al. 2018

Chemistry A European J

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“…[3][4][5][6][7] Because of these experimental studies, a number of researchers have made an effort to theoretically explain the magnetic field effects on the chemical reactions. [8,9] Thanks to these and the subsequent efforts, we are now able to explain systematically magnetic field effects in terms of the radical pair mechanism. The radical pair mechanism was then successfully applied to explain the chemically induced nuclear polarization and electron polarization, which were shown to be based on the spin dynamics of radical pairs.…”

Section: Introductionmentioning

confidence: 98%

The radical pair mechanism and the avian chemical compass: Quantum coherence and entanglement

Zhang

Berman

Kais

2015

Int J of Quantum Chemistry

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We review the spin radical pair mechanism which is a promising explanation of avian navigation. This mechanism is based on the dependence of product yields on (1) the hyperfine interaction involving electron spins and neighboring nuclear spins and (2) the intensity and orientation of the geomagnetic field. This review describes the general scheme of chemical reactions involving radical pairs generated from singlet and triplet precursors; the spin dynamics of the radical pairs; and the magnetic field dependence of product yields caused by the radical pair mechanism. The main part of the review includes a description of the chemical compass in birds. We review: the general properties of the avian compass; the basic scheme of the radical pair mechanism; the reaction kinetics in cryptochrome; quantum coherence and entanglement in the avian compass; and the effects of noise. We believe that the quantum avian compass can play an important role in avian navigation and can also provide the foundation for a new generation of sensitive and selective magnetic-sensing nanodevices. V C 2015 Wiley Periodicals, Inc. DOI: 10.1002/qua.24943 Radical Pair Mechanism IntroductionA radical is an atom, molecule or ion that has unpaired valence electrons. Radicals and radical pairs often play a very important role as intermediates in thermal, radiation, and photochemical reactions. [1] The presence of unpaired electron spins in these systems allows one to influence and control these reactions using interactions between external magnetic fields and electron spins. [2] However, until 1970, most scientists believed that ordinary magnetic fields had no significant effect on chemical or biochemical reactions, as the magnetic energy of typical molecules, under ordinary magnetic fields, is much smaller than the thermal energy at room temperature and is much smaller than the activation energies for those reactions. [1,2] This situation changed significantly in the 1970s after a series of experimental results were reported on magnetic field effects on chemical reactions. [3][4][5][6][7] Because of these experimental studies, a number of researchers have made an effort to theoretically explain the magnetic field effects on the chemical reactions. [8,9] Thanks to these and the subsequent efforts, we are now able to explain systematically magnetic field effects in terms of the radical pair mechanism. The radical pair mechanism was then successfully applied to explain the chemically induced nuclear polarization and electron polarization, which were shown to be based on the spin dynamics of radical pairs. [2] According to the radical pair mechanism, an external magnetic field affects chemical reactions by alternating the electron spin state of a weakly coupled radical pair, which is produced as an intermediate. The basic scheme of chemical reactions through the radical pairs is shown in Figure 1. Radical pairs are usually produced as short-lived intermediates through decomposition, electron transfer, or hydrogen transfer reactions from singlet or tr...

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“…6− The structural nature of these species is highly dependent on the concentration and pH. [47,50,51] The V 5+ ions induce the [V(OH 2 ) 6 ] 5+ solvated species that are formed in aqueous solution and are surrounded by dipolar H 2 O molecules.…”

mentioning

confidence: 99%

Two‐Dimensional Layered Hydroxide Nanoporous Nanohybrids Pillared with Zero‐Dimensional Polyoxovanadate Nanoclusters for Enhanced Water Oxidation Catalysis

Gunjakar

Hou

Pawar

et al. 2018

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The oxygen‐evolution reaction (OER) is critical in electrochemical water splitting and requires an efficient, sustainable, and cheap catalyst for successful practical applications. A common development strategy for OER catalysts is to search for facile routes for the synthesis of new catalytic materials with optimized chemical compositions and structures. Here, nickel hydroxide Ni(OH)2 2D nanosheets pillared with 0D polyoxovanadate (POV) nanoclusters as an OER catalyst that can operate in alkaline media are reported. The intercalation of POV nanoclusters into Ni(OH)2 induces the formation of a nanoporous layer‐by‐layer stacking architecture of 2D Ni(OH)2 nanosheets and 0D POV with a tunable chemical composition. The nanohybrid catalysts remarkably enhance the OER activity of pristine Ni(OH)2. The present findings demonstrate that the intercalation of 0D POV nanoclusters into Ni(OH)2 is effective for improving water oxidation catalysis and represents a potential method to synthesize novel, porous hydroxide‐based nanohybrid materials with superior electrochemical activities.

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Coordination Chemistry of Polyoxovanadates as Inorganic Ligands

Cited by 13 publications

References 122 publications

Design and Assembly of Covalently Functionalised Polyoxofluorovanadate Molecular Hybrids

Design and Assembly of Covalently Functionalised Polyoxofluorovanadate Molecular Hybrids

The radical pair mechanism and the avian chemical compass: Quantum coherence and entanglement

Two‐Dimensional Layered Hydroxide Nanoporous Nanohybrids Pillared with Zero‐Dimensional Polyoxovanadate Nanoclusters for Enhanced Water Oxidation Catalysis

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